CN1302990C - Process for preparing and controlling ordered pore structure of mesicpore molecular sieve - Google Patents
Process for preparing and controlling ordered pore structure of mesicpore molecular sieve Download PDFInfo
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- CN1302990C CN1302990C CNB2005100250474A CN200510025047A CN1302990C CN 1302990 C CN1302990 C CN 1302990C CN B2005100250474 A CNB2005100250474 A CN B2005100250474A CN 200510025047 A CN200510025047 A CN 200510025047A CN 1302990 C CN1302990 C CN 1302990C
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Abstract
The present invention relates to the preparation and a regulation and control method of a mesoporous molecular sieve ordered pore canal structure, which belongs to the technical field of inorganic nano materials. In the preparation method, Gemini16-6-16 surface active agents are used as a structure guiding agent, and ethylamine is a pH buffering agent; the mesoporous materials in highly ordered different pore canal structures are synthesized by changing the ratio of alcohol to water of cosolvents, such as two-dimensional hexagonal mesoporous MCM-41, three-dimensional cubic MCM-48, lamellar structure MCM-50 and hollow sphere structural materials. The mesoporous molecular sieve and hollow sphere materials with pore canals in different patterns have wide applications in the aspects of catalysis, sensors with molecular recognition capability, nano reactors, etc.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to the preparation and the regulate and control method of the orderly pore passage structure of mesopore molecular sieve.
Background technology
Since the successfully synthetic M41S series of the scientist mesopore molecular sieve of Mobil company in 1992, the synthetic of mesoporous material is the research focus in materials chemistry field always.Main achievement in research concentrates on new synthetic method, synthesis mechanism and the applied research of synthesizing new meso-hole structure molecular sieve.
Present synthesising mesoporous molecular sieve mainly adopts hydrothermal synthesis method, and optimizes its synthetic method at concrete target molecule sieve, for MCM-41, U.S. Pat 5108725, US5098684, domestic patent CN1500721A etc. have described building-up process, reaction reagent, constitutional features etc. respectively; J.Phys.Chem.B 2004,108,15043, and involutory respectively one-tenth such as domestic patent CN1364729A MCM-48 is described.
Simultaneously, research and control to how much patterns of mesopore molecular sieve profile also have patent report, as the rear forming of US5922299, the microemulsion method of US5492870 synthesizes hollow ball, the wide aperture SBA-15 of the different-shape that domestic patent CN1356265A employing coforming method obtains.
Mesopore molecular sieve is the novel material that grows up over past ten years, it shows its application prospects gradually in fields such as catalysis, molecular separation, transmitter, nano-reactors, the regulation and control of material resemblance are no doubt important, but its basic key is the synthetic and control of the orderly pore passage structure of mesopore molecular sieve, although being arranged at present, certain methods can synthesize target duct molecular sieve, but must adopt different tensio-active agents to different pore passage structures is structure directing agent, process is complicated, yet there are no report for effective control method of pore passage structure.
Summary of the invention
The object of the invention is to propose a kind of simple method that can synthesize and regulate and control the mesopore molecular sieve pore passage structure, so that according to different application requiring, the synthetic different mesopore molecular sieve of pore passage structure in order, as the hexagonal mesoporous MCM-41 of two dimension, three-dimensional cubic MCM-48, laminate structure MCM-50 and hollow ball structure material.
As structure directing agent, ethamine is the pH buffer reagent with Gemini tensio-active agent GEM16-6-16 in the present invention, by changing the ratio of cosolvent ethanol/water, the orderly pore passage structure of preparation and regulation and control mesopore molecular sieve.Its step is as follows:
1, GEM16-6-16 is dissolved in the ethanol water cosolvent, under 35-40 ℃ of water-bath, is stirred to dissolving fully, be cooled to 30 ℃ again.The mol ratio of GEM16-6-16 tensio-active agent and cosolvent is 1: 60-100;
2, in step 1 solution, drip ethamine, stirred 0.5 hour;
3, accelerate stirring velocity, in step 2 solution, slowly drip tetraethoxy, after dropwising, continue to stir 2 hours down at 30 ℃.The mol ratio of GEM16-6-16/ tetraethoxy is 0.03-0.06;
4, the reaction solution that contains white solid that step 3 is obtained was transferred to from pressing in the reactor, 100 ℃ of following hydro-thermals 48 hours;
5, step 4 is obtained reaction solution separation, washing, drying.
The cosolvent that the present invention adopts, when the mol ratio of ethanol/water is 0-0.05, obtained two-dimentional hexagonal mesoporous MCM-41 molecular sieve, increase the alcoholic acid ratio, when the mol ratio of ethanol/water is 0.06-0.08, obtained three-dimensional cubic MCM-48 molecular sieve, continuing increases the alcoholic acid ratio, when the mol ratio of ethanol/water is 0.10-0.20, obtained laminate structure MCM-50 molecular sieve, when proportion of ethanol continuation rising, during the mol ratio 0.30-0.40 of ethanol/water, obtained hollow ball material.
The present invention only adopts a kind of superficiality agent GEM16-6-16 as structure directing agent, and adds dosage and silicon source mol ratio and only be 0.03-0.06, just can obtain the material of the orderly pore passage structure of various differences.
The present invention adopts ethamine regulation and control pH, and the mol ratio of ethamine/tetraethoxy is 0.6, in the building-up process, need not to add the pH regulator agent, and makes the pH of system keep being stabilized in about 11.
The used Gemini tensio-active agent of the present invention synthesizes by following method: 1, the N of adding excessive 5%～10% in the ethanolic soln of 6-dibromo-hexane (production of Fang Qiao chemical plant, Yixing, Jiangsu), N-dimethyl hexadecylamine (Shanghai Jingwei Chemical Co., Ltd.'s production) cocurrent flow 48h.Product obtains tensio-active agent GEM16-6-16 with ethanol-ethyl acetate mixed solvent recrystallization 3～4 times, and its molecular structural formula is as follows:
But also reference Zana R., Benrraou M., Rueff R., Alkanediyl-.alpha., .omega.-bis (dimethylalkyl-ammoniumbromide) surfactants.1.Effect of the spacer chain length on the critical micelle concentration andmicelle ionization degree, Langmuir[J], 1991,7,1072-1075.
Description of drawings
Fig. 1 is the XRD diffractogram of embodiment 1 products obtained therefrom, tests CuK on the D8 of Bruker company type x-ray diffractometer
αBe gamma ray source, pipe is pressed 40KV, pipe stream 200mA.
Fig. 2 is the XRD diffractogram of embodiment 2 products obtained therefroms, tests CuK on the D8 of Bruker company type x-ray diffractometer
αBe gamma ray source, pipe is pressed 40KV, pipe stream 200mA.
Fig. 3. be the XRD diffractogram of embodiment 3 products obtained therefroms, on the D8 of Bruker company type x-ray diffractometer, test CuK
αBe gamma ray source, pipe is pressed 40KV, pipe stream 200mA.
Fig. 4. be the XRD diffractogram of embodiment 4 products obtained therefroms, on the D8 of Bruker company type x-ray diffractometer, test CuK
αBe gamma ray source, pipe is pressed 40KV, pipe stream 200mA.
Fig. 5. be the XRD diffractogram of embodiment 5 products obtained therefroms, on the D8 of Bruker company type x-ray diffractometer, test CuK
αBe gamma ray source, pipe is pressed 40KV, pipe stream 200mA.
Fig. 6 is the XRD diffractogram of embodiment 6 products obtained therefroms, tests CuK on the D8 of Bruker company type x-ray diffractometer
αBe gamma ray source, pipe is pressed 40KV, pipe stream 200mA.
Fig. 7 is the TEM figure of embodiment 7 products obtained therefroms, on the JEM-1200EXII of JEOL company type transmission electron microscope, observes, and with ethanol dispersion medium.
Fig. 8 is the TEM figure of embodiment 8 products obtained therefroms, on the JEM-1200EXII of JEOL company type transmission electron microscope, observes, and with ethanol dispersion medium.
Embodiment
Below by embodiment the present invention is further elaborated, embodiment is for understanding the unrestricted interest field of invention.
[embodiment 1] is dissolved in 1.15gGEM16-6-16 in the 90g water.Under 35-40 ℃ of water-bath, be stirred to dissolving fully, be cooled to 30 ℃ again.Drip ethamine 1ml, stirred 0.5 hour.Slowly drip tetraethoxy 5.21g, after dropwising, continue down to stir 2 hours at 30 ℃.To contain the white solid reaction solution and transfer to from pressing in the reactor, 100 ℃ of following hydro-thermals 2 days.
The product that obtains is indicated as typical MCM-41 molecular sieve structure through the XRD diffraction.As Fig. 1.
[embodiment 2] are dissolved in 1.15gGEM16-6-16 in the ethanol/water cosolvent.Under 35-40 ℃ of water-bath, be stirred to dissolving fully, be cooled to 30 ℃ again.Drip ethamine 1ml, stirred 0.5 hour.Slowly drip tetraethoxy 5.21g, after dropwising, continue down to stir 2 hours at 30 ℃.To contain the white solid reaction solution and transfer to from pressing in the reactor, 100 ℃ of following hydro-thermals 2 days.
Wherein to add dosage be 10.0g to ethanol, and the dosage that adds of water is 80.0g.
The product that obtains is indicated as typical MCM-41 molecular sieve structure through the XRD diffraction.As Fig. 2.
[embodiment 3] only change the proportioning of second alcohol and water in the cosolvent with embodiment 2 operation, and wherein to add dosage be 12.0g to ethanol, and the dosage that adds of water is 78.0g.
The product that obtains is indicated as typical MCM-48 molecular sieve structure through the XRD diffraction.As Fig. 3.
[embodiment 4] only change the proportioning of second alcohol and water in the cosolvent with embodiment 2 operation, and wherein to add dosage be 15.0g to ethanol, and the dosage that adds of water is 75.0g.
The product that obtains is indicated as typical MCM-48 molecular sieve structure through the XRD diffraction.As Fig. 4.
[embodiment 5] only change the proportioning of second alcohol and water in the cosolvent with embodiment 2 operation, and wherein to add dosage be 20g to ethanol, and the dosage that adds of water is 70g.
The product that obtains is indicated as stratiform MCM-50 molecular sieve structure through the XRD diffraction.As Fig. 5.
[embodiment 6] only change the proportioning of second alcohol and water in the cosolvent with embodiment 2 operation, and wherein to add dosage be 30g to ethanol, and the dosage that adds of water is 60g.
The product that obtains is indicated as stratiform MCM-50 molecular sieve structure through the XRD diffraction.As Fig. 6.
[embodiment 7] only change the proportioning of second alcohol and water in the cosolvent with embodiment 2 operation, and wherein to add dosage be 40g to ethanol, and the dosage that adds of water is 50g.
The product that obtains, transmission electron microscope is shown as hollow ball structure, the about 500nm of external diameter.As Fig. 7.
[embodiment 8] only change the proportioning of second alcohol and water in the cosolvent with embodiment 2 operation, and wherein to add dosage be 45g to ethanol, and the dosage that adds of water is 45g.
The product that obtains, transmission electron microscope is shown as hollow ball structure.As Fig. 8.
Claims (6)
1, the method for a kind of preparation and controlling ordered pore structure of mesicpore molecular sieve, it is characterized in that with tensio-active agent GEM16-6-16 be structure directing agent, ethamine is the pH buffer reagent, by changing the ratio of cosolvent ethanol/water, the orderly pore passage structure of control mesopore molecular sieve, its step is as follows:
(1) GEM16-6-16 is added in the ethanol water cosolvent, be stirred to dissolving fully under 35-40 ℃ of water-bath, the mol ratio of ethanol/water is 0--0.40 in the cosolvent, and the mol ratio of GEM16-6-16 tensio-active agent and cosolvent is 1: 60-100,
(2) in step 1 solution, add ethamine, stirred 0.5 hour,
(3) in step 2 solution, add tetraethoxy, continue to stir 2 hours down at 30 ℃, the mol ratio of GEM16-6-16 and tetraethoxy is 0.03-0.06,
(4) reaction solution that contains white solid that step 3 is obtained is transferred to from pressing in the reactor, 100 ℃ of following hydro-thermals 48 hours,
(5) step 4 is obtained reaction solution separation, washing, drying.
2, method for preparing medium pore molecular sieve according to claim 1 is characterized in that ethamine adds dosage and silicon source mol ratio is 0.6.
3, method for preparing medium pore molecular sieve according to claim 1 is characterized in that the cosolvent that adopts when the mol ratio of ethanol/water is 0-0.05, having obtained two-dimentional hexagonal mesoporous MCM-41 molecular sieve.
4, method for preparing medium pore molecular sieve according to claim 1 is characterized in that the cosolvent that adopts when the mol ratio of ethanol/water is 0.06-0.08, having obtained three-dimensional cubic MCM-48 molecular sieve.
5, method for preparing medium pore molecular sieve according to claim 1 is characterized in that the cosolvent that adopts when the mol ratio of ethanol/water is 0.10-0.20, having obtained laminate structure MCM-50 molecular sieve.
6, method for preparing medium pore molecular sieve according to claim 1 is characterized in that the cosolvent that adopts, when the mol ratio 0.30-0.40 of ethanol/water, has obtained hollow ball.
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| CN109665542B (en) * | 2017-10-17 | 2022-07-12 | 中国石油化工股份有限公司 | Layered molecular sieve and preparation method thereof |
| CN108568309B (en) * | 2018-04-26 | 2020-10-09 | 济南大学 | Oil product deep hydrodesulfurization catalyst and preparation method thereof |
| CN108435233B (en) * | 2018-04-26 | 2020-07-28 | 济南大学 | Method for improving deep hydrodesulfurization of oil product |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492870A (en) * | 1994-04-13 | 1996-02-20 | The Board Of Trustees Of The University Of Illinois | Hollow ceramic microspheres by sol-gel dehydration with improved control over size and morphology |
| JP2001247309A (en) * | 2000-01-20 | 2001-09-11 | Chinese Petroleum Corp | Hydrothermally stable metal-containing mcm-41 type intermediate fine pore molecular sieve |
| JP2001302231A (en) * | 2000-04-27 | 2001-10-31 | Chinese Petroleum Corp | Metal-containing mcm-41 molecular sieve having medium pore diameter and high hydrothermal stability |
| CN1356265A (en) * | 2001-08-20 | 2002-07-03 | 复旦大学 | Process for preparing shape-controllable big-pore mesoporous molecular sieve |
| CN1500721A (en) * | 2002-11-13 | 2004-06-02 | 中国石油化工股份有限公司 | Process for preparing pure silicon MCM-41 molecular sieves |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492870A (en) * | 1994-04-13 | 1996-02-20 | The Board Of Trustees Of The University Of Illinois | Hollow ceramic microspheres by sol-gel dehydration with improved control over size and morphology |
| JP2001247309A (en) * | 2000-01-20 | 2001-09-11 | Chinese Petroleum Corp | Hydrothermally stable metal-containing mcm-41 type intermediate fine pore molecular sieve |
| JP2001302231A (en) * | 2000-04-27 | 2001-10-31 | Chinese Petroleum Corp | Metal-containing mcm-41 molecular sieve having medium pore diameter and high hydrothermal stability |
| CN1356265A (en) * | 2001-08-20 | 2002-07-03 | 复旦大学 | Process for preparing shape-controllable big-pore mesoporous molecular sieve |
| CN1500721A (en) * | 2002-11-13 | 2004-06-02 | 中国石油化工股份有限公司 | Process for preparing pure silicon MCM-41 molecular sieves |
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